TY - JOUR
T1 - α-Acyloxynitroso dienophiles in [4+2] hetero Diels–Alder cycloadditions: mechanistic insights
AU - Calvet, Geraldine
AU - Coote, Susannah
AU - Blanchard, Nicolas
AU - Kouklovsky, Cyrille
PY - 2010/2/23
Y1 - 2010/2/23
N2 - α-Acyloxynitroso derivatives are a class of heterodienophiles leading to valuable 3,6-dihydro-1,2-oxazines or the corresponding aminoalcohols in good yields. The discovery that a β-oxygenated moiety led to a domino [4+2] cycloaddition/σN–O bond cleavage in the presence of a catalytic amount of Lewis acid was investigated in detail, through kinetic profiling of the reaction both in the absence and presence of a promoter. These studies showed that the role of the Lewis acid was to accelerate the σN–O bond cleavage thereby promoting a highly reproducible sequence. In addition, our preliminary results on an asymmetric version of this domino sequence are reported.
AB - α-Acyloxynitroso derivatives are a class of heterodienophiles leading to valuable 3,6-dihydro-1,2-oxazines or the corresponding aminoalcohols in good yields. The discovery that a β-oxygenated moiety led to a domino [4+2] cycloaddition/σN–O bond cleavage in the presence of a catalytic amount of Lewis acid was investigated in detail, through kinetic profiling of the reaction both in the absence and presence of a promoter. These studies showed that the role of the Lewis acid was to accelerate the σN–O bond cleavage thereby promoting a highly reproducible sequence. In addition, our preliminary results on an asymmetric version of this domino sequence are reported.
UR - https://www.scopus.com/pages/publications/77949568646
U2 - 10.1016/j.tet.2010.02.065
DO - 10.1016/j.tet.2010.02.065
M3 - Article
SN - 0040-4020
VL - 66
SP - 2969
EP - 2980
JO - Tetrahedron
JF - Tetrahedron
IS - 16
ER -